DE2312971A1 - MODIFIED POLYARYLENE-POLYAETHERIC RESIN COMPOSITIONS - Google Patents

Description

Modified polyarylene-polyether resin compositions

The invention relates to polyarylene-polyether resin compositions, which are characterized by improved impact resistance and fire resistance. The invention relates in particular to thermoplastic resin blends of a polyarylene-polyether resin with a poly (epihalohydrin) ·.

The polyarylene polyether resins are known and described in numerous publications such as US Patents 3,264,536 and 3,423,479. The high molecular weight polymers are thermoplastics with good technical properties. They have relatively high softening points, ie about 135 ⁰ C (275 ° F), and they have excellent dimensional stability.

However, the impact resistance or fire resistance of the polyarylene-polyether resins is insufficient to make them to be used in areas of application where they could otherwise be used to advantage.

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_ 9 -

The invention relates to mixtures of polyarylene polyether resins high molecular weight and 2 to 25% (all percentages are in the present application expressed by weight) of poly (epihalohydrins), which are characterized by significantly improved impact resistance and fire resistance are characterized. The incorporation of these chlorinated polyethers detracts from the desirable properties of the polyarylene-polyether resins, i.e., the high heat distortion temperature and the mechanical strength properties of the resin, are not disadvantageous.

The polyarylene-polyether resins of the present invention . contain repeating units that can be represented by the following general formula:

—E O A O B - ^, (I)

wherein

A is the residue of a "dihydric phenol, B is the residue of a benzenoid compound acting as a substituent contains an inert electron withdrawing group, and

η is an integer and is at least 15 and is preferably 20 or higher, and where both of the residues are covalently bonded through oxygen ether atoms.

The dihydric phenol radical (A) can, for example, be a mononuclear phenylene group or a di-, tri- or be polynuclear phenylene group. The divalent phenol residue may optionally be substituted with an inert substituent on the nucleus such as halogen, alkoxy, alkyl, etc. be.

The dihydric phenol which supplies the radical A is preferably a weakly acidic dihydric di- or trinuclear phenol such as, for example, the dihydroxydiphenylalkanes or dihydroxydiphenyl-p-dialkylbenzenes or those substituted on the nucleus; Derivatives thereof. Suitable dihydric phenols are, for example, 2 * 2-bis (4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) -2-phenylethane, α, cc-bis - (4-hydroxyphenyl) -p-diisopropylbenzene, α, oc-bis- (4-hydroxyphenyl) -p-xylene, etc. Suitable dihydric phenols halogenated on the nucleus are, for example, 2,2-bis- (3,5-dichloro- 4-hydroxyphenyl) propane, _t 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane, etc. Other suitable di-, tri- or polynuclear phenols are those in which the phenol radicals have functional groups which contain a hetero atom such as ether oxygen (- 0 -), carbonyl (- CO -), sulfide (- S -), sulfon (- SO ₂ -), etc. are bound.

A mixture of two or more different dihydric phenols can be used in the invention Mixtures can be used. In the polymer formula (I) means

309839/0964

A is one or two or more different aromatic radicals. The term "A" as used in the present application is used means the remainder of a dihydric phenol after removal of the hydrogen of the two aromatic ones Hydroxyl groups. Thus, the polyarylene polyethers contain repeating groups of the dihydric phenol radical and the rest of the benzenoid compound, which is bound via aromatic ether oxygen atoms.

The berizenoid radical (B) can be derived from any benzenoid dihalogen compound in which two halogen atoms are bonded to benzene rings which contain at least one electron withdrawing group in at least one of the o- and p-positions, based on the halogen atom. Such benzenoid dihalogen compounds can either be mononuclear; the halogen atoms are bonded to the same benzenoid ring, or they can be polynuclear, the halogen atoms being bonded to different benzenoid rings, provided that the activating, electron-withdrawing group is in the o- or p-position of this benzenoid nucleus. The more reactive halogens, chlorine and fluorine, are the preferred halogen substituents. The electron withdrawing group is preferably a strongly activating group such as a sulfon (- SO ₂ -), ketone (-CO -), sulfoxide (- SO -), Vinyl (- CH = CH -) or azo group (-N = N-).

39/0966

If desired, one can prepare polymers from mixtures of two or more benzenoid dihalogen compounds, each of the polymers having the structure described in the previous section. In the polyra formula (I) B can be the same or different. In the present application, B denotes an aromatic or benzenoid Residue of a compound after removal of the halogen atoms on the benzenoid nucleus.

Preferred polyarylene polyether resins contain repeating units of the formula (II

v / o r in

C is a divalent linking group,

D a strongly activating, electron withdrawing group,

X. and X ^ inert nuclear halogen, alkyl or alkoxy substituents and

c and d integers with a value from 0 up to and including 4 mean.

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Most preferred are polyarylene polyether resins of the formula (II) in which C is a divalent alkyl or benzenoid p-dialkyl group, D is a sulfone (- SQ ₂ -) group, and c and d are 0.

Typical examples of polyarylene-polyether resins and processes for their preparation are described, for example, in US Pat U.S. Patents 3,264,536 and 3,423,479 and in New Linear Polymers, Chapter 5, described by Leet et Al.

The epichlorohydrin polymers used in the present invention are polyethers containing halomethyl groups, bonded to the main polymer chain, as represented by the following general formula (Hl)

CH ₂ X

wherein X is a halogen atom such as a bromine, fluorine, chlorine or iodine atom. A preferred epihalohydrin polymer is poly (epichlorohydrin). Alternatively, the epihalohydrin polymers can be copolymers which contain at least 50% epihalohydrin units as described above, the remainder of one or more alkylene epoxides such as ethylene oxide, propylene oxide, butene oxides, etc., butadiene monoxide, cyclohexenoxy, vinyl cyclohexene oxide, epoxy ethers such as ethyl glycol,

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2-chloroethyl glycidyl ether, hexyl glycidyl ether, allyl glycidyl ether can exist, among other things.

The epihalohydrin polymers useful in making the novel compositions of the present invention are well known and are commercially available. This Epihalogenhydrinpolymere for example, are described in detail in US Patent 3,026,270.

In the compositions of the invention, the poly (epihalohydrin) is in an amount from about 2 to 25% by weight, based on the mixture, and preferably in an amount of approximately 5 to 15/6, based on the mixture. Accordingly, the polyarylene-polyether resin is in an amount of at least 75%, based on the mixture, and more preferably contained in the mixture in an amount of about 85 to 95%, based on the mixture.

The method used to mix the polyarylene-polyether resin used with the poly (epihalohydrin) is not critical. Preferably the resin and the chlorinated poly (epihalohydrin) ethers physically mixed using mechanical mixing devices, which are usually used for mixing rubbers or plastics such as extruders, Banbury mixers or Differential roller mills. To ensure good mixing of the polymers to facilitate and to achieve the desired improved combination

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In order to maintain physical properties, mechanical blending is carried out at temperatures sufficiently high to soften the polymers so that they are well dispersed and blended together.

Alternatively, the resin and the poly (epihalohydrin) mixed in solution by putting the polymers in one. Solvent such as dimethylformamide dissolves and then the polymer mixture precipitates by adding the solution to a non-solvent such as isopropanol, wherein a homogeneous mixture is obtained, which is then dried by a suitable method. The mix can be at deformed at a temperature above their softening point.

The mixtures according to the invention can contain certain other additives in order to soften the resin mixtures, to lubricate, to color, to pigment, the oxy-

t - ■

to prevent dation, etc. Such additives are well known and can be incorporated into the mixtures of the invention will.

The invention provides a new class of polyarylene-polyether resin mixtures, which is characterized by a unique combination of physical properties are. In particular, thermoplastic compositions are obtained which have significantly improved impact resistance and fire resistance

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have persistence. Incorporation of a poly (epihalohydrin) affects the high heat distortion temperature or other mechanical strength properties of the Polyarylene-polyether resins are not disadvantageous.

The following examples illustrate the invention without to restrict them.

The test results reported in the following examples were made according to the following ASTM procedures obtain:

Notched Izod Impact Strength D256A-56

Flexural module D790-66

Tensile strength D638-64T

Heat distortion temperatures at

18.5 kg / cm ² = 264 psi) D648-56

Fire resistance Federal Standard

191-5903

example 1

5, 10, 15 and 20% by weight of poly (epichlorohydrin) homopolymer were mixed with a polyarylene polyether resin. The poly (epichlorohydrin) has the designation Hydrin ^ '100 and is manufactured by the BF Goodrich Co. The poly (epichlorohydrin) has a specific gravity of 1.36 (20 ° c) and a Mooney viscosity of 60 (ML 4 at 10O ⁰ C). The polyarylene-polyether resin is available from Union Carbide Corp. sold under the trademark Bakelite Polysulfone P-1700 and it

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is the condensation polymer of 4,4'-diehlordiphenyl sulfone and the sodium salt of bisphenol A. The polyarylene polyether resin "has a specific gravity of 1.24 (20 ^° C.) and a melt flow index of 6.5 (g / 10 min).

Mixing was done with a Banbury internal shear mixer. The poly (epichlorohydrin) and the polyarylene polyether resin were mixed in the molten state at or above a temperature of 232 ⁰ C (450 ⁰ F) and with an average shear value of 300 seconds. A mixing time of about 7 minutes was sufficient to give a homogeneous mixture of the poly (epichlorohydrin) and the resin matrix. The mixtures were then calendered into sheet, were molded from the plates was 24.6 kg / crn ^ (350 psi) and 260 ⁰ C (50O ⁰ F) under pressure. Test specimens were machine cut from these panels. The physical test results are summarized in Table I.

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Table I.

Comparison of the properties of the resin and the polymer mixture

Weight $ PoIy-

(epichlor-

hydrin)

Notched Izod Strength cm.kg/cm notch (ft.lbs / in.)

Heat distortion temperature
⁰ C ( ⁰ F)

Bend-Zugfe- extinguishing time

module «stigk * (flame-out

kg / cm kg / cm time)

(psi) (vsi) (see)

ω ο co

O co o>

comparison

PSO P-1700 Composition A.

B C D

10 15 20

4.38 (0.8)

5.43 (1.0)

52.9 (9.7)

38.2 (7.1)

21.8 (4.0)

172
(341)

171
(340)

169
(337)

165
(329)

149.5
(301)

26 200 770 (373 000) (10 900)

27 000 809

(384 000) (11 500)

21 300 612

(303 000) (8 700)

20 950 570

(298 000) (8 100)

17 750 478

(252 000) (6 800)

40

5,

5 ^

⁵ co

From Table I it can be seen that the addition of a poly (epichlorohydrin) greatly improves the impact resistance of the polyarylene-polyether resins. The extinguishing time or flame-out time listed shows that the compositions of the invention have significantly improved flame resistance when compared to the unmodified polyarylene-polyether resins. The incorporation of the poly (epichlorohydrin) does not adversely affect the high heat distortion temperature or other mechanical strength properties of the polyarylene-polyether resin.

Example 2

5, 10, 15 and 20% by weight of poly (epichlorohydrin-coethylene oxide) copolymer were mixed with a polyarylene-polyether resin. This particular chlorinated polyether bears

(R)

is called Hydrin ^v 'and is manufactured by BFGoodrich Co. The poly (epichlorohydrin-co-ethylene oxide) copolymer has a specific gravity of 1.27 (20 ⁰ C) and a Mooney viscosity of 100 (MLA at 100 ⁰ C). The resin described in Example 1 was used as the polyarylene polyether resin.

Mixing was done with a Banbury internal shear mixer. The epichlorohydrin copolymer and the polyarylene polyether resin were in the molten state at or above a temperature of 232 ° C (450 ⁰ F) and'einer, durch-

309839/096 U

average shear number * of 300 seconds ". A mixing time of approximately 7 minutes was sufficient to give a homogeneous mixture of the epichlorohydrin copolymer and the resin matrix. The mixtures were then calendered into sheet material, from the plate under pressure at 24.6 kg / cm ² (350 psi) were deformed at 260 ° C (500 ° F).

The test samples were machine cut from these panels. The physical test results are summarized in Table II.

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Table II Comparison of the properties of the resin and the poly blend

Notched Izod Strength cm.kg/cm notch (ft. lbs./in.)

# PoIy-

'(epichlorohydrin)

Heat loss Bending Tensile strength shaping modulp speed ρ temperature kg / cm kg / cm ⁰ C ( ⁰ F) (psi) (psi)

Deletion time

(lake)

OO U) CD

Comparison PSO-PI700

Composition I

10

K L

4.38 (0.8)

6.6 (1.2)

46.2 (8.5)

41.6 (7.6)

18.0 (3.3)

172 (341) 26,200

(373 000)

170 (339) 27,400

(390 000)

165 (331) 22,400

(319 000)

162 (323) 19,900

(282 000)

141 (287) 17,850

(254 000)

770 (10 900)

773 (11,000)

591 (8 400)

450 (6400)

366 (5,200)

i \ J CO

From Table II it can be seen that the addition of poly (epichlorohydrin-co-ethylene oxide) copolymer increases the impact strength of the polyarylene-polyether resin is greatly improved. The flash-out or extinguishing times show that the inventive Compositions have substantially improved fire resistance compared to the unmodified Polyarylene polyether resin. The incorporation of the chlorinated polyether resin affects the high heat distortion temperature or other mechanical strength properties of the polyarylene-polyether resin are not disadvantageous.

Example 3

A mixture of a polyarylene polyether resin with 2.5% poly (epichlorohydrin) and 2.5% poly (epichlorohydrinco-ethylene oxide) The epichlorohydrin polymers described in Examples 1 and 2, respectively, were prepared in a manner similar to previously described and then samples were prepared therefrom. This composition had impact resistance of 30.5 cm kg / cm (5.6 ft.lbs./in.) notch and a flame-out time of 7 seconds, a large improvement with the properties of the unmodified polyarylene-polyether resin.

Example 4

A mixture of polyarylene polyether resin with 3% poly (epichlorohydrin) and 5% poly (epichlorohydrin-co-ethylene-

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oxyd) y the epichlorohydrin polymers are in Examples 1 or 2, was processed in a manner similar to that described above and then samples were made therefrom, The composition had an impact strength of 19.0 cm kg / cm (3.5 ft.lbs./in.) notch and a 5 second flame-out time, a large improvement compared to properties of the unmodified polyarylene polyether resin.

Because of their unique combination of physical Properties and because of excellent fire resistance, the mixtures of the invention find many and varied Applications. For example, they can be in powder form formulations either alone or mixed with various Fillers such as with wood, flour, kieselguhr, carbon black, silicon dioxide etc. are used to make molded parts such as. . Dishes, devices, wheels, gears, trunnions, bearings, bushings, bearings, running bearings, tapes and resin disks, Manufacture stools, curved bodies, steering fingers, especially for applications where high impact strengths and good Fire resistance are required. You can .used can be used to make shaped, calendered or extruded articles and they can find a variety of uses in form of films, webs, rods, tapes, etc. The compositions can also with various modifying agents such as mixed with dyes, pigments, stabilizers, plasticizers, hardeners, etc.

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Claims (11)

Claims 1. Thermoplastic resin composition, characterized in that it contains: A) about 75 "to 98 weight percent of a linear thermoplastic Polyarylene-polyether polysulfone and B) accordingly approximately 2 to 25% by weight of an elastomer such as a poly-cepihalohydrin) and / or Copolymers of an epihalohydrin with at least one another vicinal monoepoxide, being the epihalohydrin repeating units in the polymer the formula -CH - CHo - 0 CH ₀ X have, wherein X is a halogen such as a bromine, fluorine, chlorine or Means iodine atom, and wherein the units copolymerize with the vicinal monoepoxide are bound via the oxygen atoms of the epoxide ring of the vicinal monoepoxide. 2. Composition according to claim 1, characterized in that at least 10% of the bonds between the arylene groups in (A) are sulfonic groups. 3. Composition according to claim 1, characterized in that that the thermoplastic polyarylene polyether 309839/0964 Polysulfone resin contains alkylidene bonds between the arylene groups. · 4. Composition according to claim 1, characterized in that - indicates that (A) repeating units of the formula -E- -B- ⁿ contains where A is the remainder of a dihydric phenol and B is the remainder of a benzenoid compound, the one contains inert, electron withdrawing group in at least one of the o- or p-positions to the valence bonds, mean, both radicals being divalent to the ether oxygen atoms via aromatic carbon atoms, and in which η means a positive integer and is at least 15 and wherein at least one of groups A and B provides a sulfone bond between aromatic carbon atoms. 5. Composition according to claim 1, characterized .gekisiert, that (A) repeating units of the formula (X ₁ ) 309839/0964 contains where C is a bond between aromatic carbon atoms and / or a divalent connecting group, D mean a suIfon X ^ and Xp de inert substituents such as halogen atoms, Denote alkyl groups with 1 "to 4 carbon atoms and alkoxy groups with 1 to 4 carbon atoms and c and d represent integers with a value from 0 to 4, inclusive. 6. Composition according to claim 5, characterized in that (A) repeating units of the formula contains. 7. Composition according to claim 6, characterized in that (A) in an amount * of about 80 to 95 wt. based on the mixture in which the mixture is contained. 8. Composition according to claim 6, characterized in that (B) is poly (epihalohydrin). 309839/0964 9. Composition according to claim 6, characterized in that (B) is a copolymer of an epihalohydrin and at least one other vicinal monoepoxide. 10. Composition according to claim 6, characterized in that that (B) means poly (epichlorohydrin) ". 11. 'Composition according to claim 6, characterized in that that (B) is a copolymer of epichlorohydrin and ethylene oxide. 309839 / 096Λ